metals

Review
Research Progress in Preparation and Purification of
Rare Earth Metals
Hang Liu 1 , Yao Zhang 2 , Yikun Luan 1, *, Huimin Yu 3 and Dianzhong Li 1
1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China;
liuhang@imr.ac.cn (H.L.); dzli@imr.ac.cn (D.L.)
2 Baotou Rare Earth R&D Center, Chinese Academy of Sciences, Baotou 014000, China; zhangyao@btzkxt.cn
3 School of Metallurgy, Northeastern University, Shenyang 110819, China; hmyu@ire.ac.cn
* Correspondence: ykluan@imr.ac.cn




Received: 28 August 2020; Accepted: 9 October 2020; Published: 15 October 2020


Abstract: The purity of rare earth metals is one of the most important factors to research and develop
high technique materials. However, high purity rare earth metals are not easily achieved. This review
summarizes the preparation and purification methods of rare earth metals. First, the preparation
principle and process of molten salt electrolysis and metal thermal reduction are introduced. The main
sources of metallic impurities and interstitial impurities in rare earth metals as well as the action
mechanism of reducing the concentration of different impurities are analyzed and summarized. Then,
the purification principle and process of vacuum distillation, arc melting, zone melting, and solid state
electromigration are also discussed. Furthermore, the removal effect and function rule of metallic
impurities and interstitial impurities in rare earth metals are outlined. Finally, the crucial issues in the
development of high purity rare earth metals are put forward, and the development direction of high
purity rare earth metals in future are pointed out on this basis.

Keywords: rare earth metals; purity; impurity concentration; preparation; purification

1. Introduction
Rare earth element (named as RE) is the general name of 17 special elements, containing lanthanide
element, scandium, and yttrium. They have been widely applied in functional materials, steel,
and nonferrous metals because of their special optical, electrical, and magnetic properties. In particular,
RE functional materials and structure materials play an important role in the development of aerospace
industry, military equipment [1], domestic appliances [2], new energy saving, and environmental
technologies [3,4]. For example, neodymium and samarium are the main components of NdFeB
permanent magnets and SmCo permanent magnets respectively. Furthermore, magnetic energy
product of RE permanent magnet materials is much higher than that of ferrite and Al-Ni-Co permanent
magnet materials [5,6]. Therefore, RE permanent magnet materials have been proverbially used in
air conditioning, sound box, and permanent magnet motor. Terbium and dysprosium are the main
ingredients of magnetostrictive materials, and the magnetostrictive coefficient is superior than that
of Fe-Ni-Co alloy. In addition, RE magnetostrictive materials have been widely used in high-power
emitting sonar, sensor, and communications. RE hydrogen storage alloy shows the advantages of high
electric capacity, good stability, high hydrogen absorption efficiency, and no pollution, which makes
it to be widely used in the fields of battery, brake, and refrigeration [7]. The addition of rare earth
to steel can modify inclusions, refine grain, and strengthen microalloying, which can significantly
improve the fatigue performance of bearing steel [8]. The purity of rare earth metals is the key factor
affecting the performance of functional materials and structural material. For example, high oxygen
concentration of rare earth metals could weaken the intrinsic coercivity of RE permanent magnet

Metals 2020, 10, 1376; doi:10.3390/met10101376 www.mdpi.com/journal/metals

Metals 2020, 10, x FOR PEER REVIEW 2 of 12

intrinsic
Metals 2020, coercivity
10, 1376 of RE permanent magnet materials. Low purity rare earth metals may 2cause of 13
nozzle clogging and unstable performance in continuous casting process of RE steel. Specially,
magnetostrictive materials and sputtering target materials require the purity of rare earth metals to
materials. Low 99.99%
be higher than purity rare earth
[9,10]. Themetals
purity may cause
of rare nozzle
earth clogging
metals shouldand unstable
exceed 99.95%performance
in permanent in
continuous casting process of RE steel. Specially, magnetostrictive materials and sputtering
magnetic materials [11]. In recent years, the preparation and purification of high-purity rare earth target
materials require
metals has the purity
attracted of rare earth
more attention from metals to be higher
governments andthan 99.99%
experts. The[9,10]. The departments
relevant purity of rare of
earth
the
metals should exceed 99.95% in permanent magnetic materials [11]. In recent years, the
United States, Japan, and other countries have even listed RE products as the key strategic elements preparation
and purification
for the of high-purity
development of militaryraretechnology
earth metalsandhashigh
attracted more industries.
technique attention from
With governments
the progress and of
experts.
science The
and relevant departments
technology, of therare
high purity United States,
earth Japan,
metals and
play a other countries
critical role in have even economic
national listed RE
products as the
construction andkey strategic
daily elements for the development of military technology and high technique
life [12,13].
industries. With the progress of science and technology, high purity rare earth metals play a critical
role in national
2. Progress economic construction
in Preparation of Rare Earth andMetals
daily life [12,13].

With the
2. Progress in wide applications
Preparation of rare
of Rare earth
Earth metals, the increasing demand for high-purity rare earth
Metals
metals has stimulated the rapid development of preparation technology. At present, molten salt
With theand
electrolysis wide applications
metal of rare earth
thermal reduction aremetals, the increasing
the common methods demand for high-purity
for preparing raremetals.
rare earth earth
metals has stimulated the rapid development of preparation technology. At present,
In principle, these two methods can extract all kinds of rare earth elements. Light rare earth metals molten salt
electrolysis and metal thermal reduction are the common methods for preparing rare
such as La, Ce, Pr, and Nd are produced by molten salt electrolysis for considering economic cost earth metals.
In principle,
factors such these
as fixedtwoasset
methods can extract
investment, raw all kinds ofand
materials, rareenergy
earth elements. Light
consumption rareMetal
[14]. earththermal
metals
such as La, Ce, Pr, and Nd are produced by molten salt electrolysis for considering
reduction method is more suitable for preparing heavy rare earth metals such as Gd, Tb, and Y with economic cost
factors such asand
high melting fixed assetpoints.
boiling investment, raw materials, and energy consumption [14]. Metal thermal
reduction method is more suitable for preparing heavy rare earth metals such as Gd, Tb, and Y with
high melting
2.1. Molten and
Salt boiling points.
Electrolysis
Several
2.1. Molten kinds
Salt of metals such as Cu, Al, and Mg are prepared by molten salt electrolysis [15–17].
Electrolysis
The preparation of rare earth metals by molten salt electrolysis started from the molten salt system
Several kinds of metals such as Cu, Al, and Mg are prepared by molten salt electrolysis [15–17].
of chloride. Because of the problems of chloride electrolysis preparation such as easy moisture
The preparation of rare earth metals by molten salt electrolysis started from the molten salt system of
absorption of raw materials, low yield and serious exhaust pollution, the preparation of rare earth
chloride. Because of the problems of chloride electrolysis preparation such as easy moisture absorption
metals by rare earth chloride was clearly banned by the state [18]. Nowadays, rare earth metals are
of raw materials, low yield and serious exhaust pollution, the preparation of rare earth metals by rare
mainly prepared by fluoride oxide electrolysis in industry [19–21]. The schematic diagram of molten
earth chloride was clearly banned by the state [18]. Nowadays, rare earth metals are mainly prepared
salt electrolysis is shown in Figure 1. RE2O3 dissolved in fluoride molten salt and dissociated into rare
by fluoride oxide electrolysis in industry [19–21]. The schematic diagram of molten salt electrolysis is
earth cations and oxygen anions. Under the action of direct current field, rare earth cations move
shown in Figure 1. RE2 O3 dissolved in fluoride molten salt and dissociated into rare earth cations
toward cathode and can be reduced to metals by obtaining electrons [22]. Oxygen anions move to the
and oxygen anions. Under the action of direct current field, rare earth cations move toward cathode
anode and lose electrons, forming oxygen or interacting with graphite to form CO2 and CO, the
and can be reduced to metals by obtaining electrons [22]. Oxygen anions move to the anode and lose
reactions that occur in this system are as follows [23]:
electrons, forming oxygen or interacting with graphite to form CO2 and CO, the reactions that occur in
this system are as follows [23]:-Cathode(reduction) reaction: RE3+ + 3e– = RE (1)
-Anode(oxidation) reaction: 2O2 − 4e– = O2(g) (2)
-Cathode(reduction) reaction: RE3+ + 3e− = RE (1)
-Reduction–oxidation (Redox) reaction: RE2O3 + C = 2RE + CO2 + CO (3)
-Anode(oxidation) reaction: 2O2 − 4e− = O2 (g) (2)
Metallic impurities such as Al, Si, Ti, W, Mo, Fe and interstitial impurities C, O, and N might
-Reduction-oxidation
exist in rare earth metals prepared by(Redox) reaction:
the above method 2 O3 + C = 2RE + CO2 + CO
RE[24,25]. (3)

Figure 1.
Figure 1. Schematic
Schematic diagram
diagram of
of molten
molten salt
salt electrolysis.
electrolysis.
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MetalsMetallic
Metals 2020, 10,
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FOR PEER
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such as Al, Si, Ti, W, Mo, Fe and interstitial impurities C, O, and N might33 exist of 12
of 12
in rare earth metals prepared by the above method [24,25].
Al
Al and
Al and
andSi SiSiimpurities
impurities mainly
impuritiesmainlymainly are
are derived
derived
are derived from
fromfromfurnace
furnace
furnace materials
materials [26][26]
[26]
materials and and
and raw raw
raw materials
materials [27]. The
[27].
materials The
[27].
concentration
concentration
The concentration of Al
of Al of and
and Si in
AlSiand rare
in rare earth
Si inearth metals
rare metals were reduced
were reduced
earth metals from 0.03%
from 0.03%
were reduced to
fromto0.03% below 0.01%
belowto0.01%
below by altering
by0.01%
altering by
the
the variety
variety
altering of
theof furnace
furnace
variety materials
of materials and the
and
furnace materials the purity
purity ofpurity
and theof raw material
raw material [26]. Carbon
[26].
of raw material Carbon impurity
[26]. impurity is mainly
is
Carbon impurity mainly related
isrelated
mainly
to
to graphite
graphite
related anode or
anode
to graphite or graphite
graphite
anode crucible,
crucible,
or graphite and iron
and
crucible, iron impurity
andimpurity
iron impuritymainlymainly
mainly came came
came from from
from anodeanode
anode clampclamp
clamp and
and
auxiliary
auxiliary
and auxiliarytools [28].
toolstools By
[28].[28].
By Byadjusting
adjusting
adjusting electrolytic
electrolytic
electrolytic bath
bath
bath structure,
structure, electrolytic
structure,electrolytic temperature
electrolytictemperature
temperatureand and other
and other
other
technical
technical parameters can control the carbon concentration in rare earth
technical parameters can control the carbon concentration in rare earth metals below 0.03% and iron
parameters can control the carbon concentration in rare earth metals
metals below
below 0.03%
0.03% and
and iron
iron
concentration
concentration
concentration belowbelow 0.3%
below 0.3% effectively
0.3% effectively [28,29].
effectively [28,29]. Moreover,
[28,29]. Moreover,
Moreover, W, W, Ti, and Mo impurities
W, Ti, and Mo impurities
impurities are are mainly
are mainly derived
mainly derived
derived
from
from metal crucible
from metal crucible and and stirring
and stirring device.
stirring device. The
device. Thetotal
The totalconcentration
total concentrationofof
concentration ofW,W,Ti,Ti,
W, Ti,and
andMo
and Mo
Mo could
could
could be
bebe reduced
reduced
reduced to
to
to below
below
below 0.05%
0.05%
0.05% bybyby adjusting
adjustingthe
adjusting the crucible
thecrucible
crucibleand and stirring
andstirring device
stirringdevice materials
devicematerials [30].
materials[30]. Impurities
[30]. Impurities of O and
Impurities of O and N are N are
are
mainly
mainly derived
mainly derived
derived fromfrom rare
from rare earth
rare earth oxide
earth oxide and
oxide and the
and the oxygen
the oxygen
oxygen in in air.
in air. The
air. The oxygen
The oxygen concentration
oxygen concentration
concentration of of commercial
of commercial
commercial
electrolysis
electrolysis rare
electrolysis rare earth
rare earth metal
earth metal was
metal was even
was even
even asas high
as high
high asas 0.1% [31].
as 0.1% [31]. In
In recent
In recent years,
recent years, researchers
years, researchers
researchers of of IMR
of IMR have
IMR havehave
explored
explored
explored thethe oxygen
the oxygen reduction
oxygen reduction methods
reduction methods
methods in in molten
in molten salt
molten salt electrolysis
salt electrolysis process,
electrolysis process,
process, and and high
and high purity
high purity rare
purity rare earth
rare earth
earth
metals
metals were successfully
metals were successfullyprepared
successfully preparedby
prepared byregulating
by regulatingtechnical
regulating technical
technical parameters,
parameters,
parameters, as
as as
shownshown
shown on
on on in Figure
in
in FigureFigure 2. the
2.
2. At At
At
the
the
samesame
same
time,time,
time,
oxygenoxygen
oxygen concentration
concentration
concentration could could
could be reduced
be reduced
be reduced to less
to
to less less than
thanthan 0.008%
0.008%
0.008% after
afterafter
usingusing
using suction
suction
suction castingcasting
casting
and
and
and airless
airless
airless shot
shotshot blasting,
blasting,
blasting, as shown
as shown
as shown in Figure
in Figure
in Figure 3 [32].
3 [32].
3 [32].

800 (b)
800 (E) 300 (b)
(E) 300
700
700
%%
%%

250
−4−4

600 250
−4−4

600
/ ×10
/ ×10

content/ ×10
content/ ×10

500 200
500 200
Oxygencontent
Oxygencontent

400
400
150
300
150
300
Oxygen
Oxygen

200 100
200 100
100
100 50
50
0
0 1000 1020 1040 1060 1080 1100 5 6 7 8 9 10
1000 1020 1040 1060 1080 1100 5 6 7 8 9 10
EEectEoEyEEE teEEeEEtEEe / ℃ REte of EddEtEon / kg·h-1
EEectEoEyEEE teEEeEEtEEe / ℃ REte of EddEtEon / kg·h-1

Figure 2.
Figure 2.
Figure Effect of
Effectof
2. Effect electrolysis
ofelectrolysis temperature
electrolysis temperature (a)
temperature (a) and
(a) and rate
and rate of
rate of addition (b)
of addition (b) on
on oxygen
oxygen concentration.
concentration.

300
300
EEctEon cEEtEng
EEctEon cEEtEng
EEnEEE cEEtEng
250 EEnEEE cEEtEng
250
%%

4
−
0
4
−
1
0 CoEEeEcEEE Re
1 CoEEeEcEEE Re
200
content/ /××

200
Oxygencontent

150
150
Oxygen

100 PEtent technoEogy Re

100 PEtent technoEogy Re

50
50

Figure 3.
Figure 3.
Figure Effect of
Effect of
3. Effect casting
of casting method
casting method on
method on oxygen
on oxygen concentration.
oxygen concentration.
concentration.

Baotou
Baotou ResearchInstitute
Baotou Research
Research Institute
Institute of Rare
of Rare
of Rare Earths
Earths successfully
successfully
Earths developed
developed
successfully aa 33 kA
kA fluorosalt
a 3 kA fluorosalt
developed fluorosalt system
system electrolytic
system
electrolytic
bath in 1984.
electrolytic bath in 1984.
After
bath in 1984. After
moreAfter more
than more
30 yearsthan 30
of30
than years of
of development,
development,
years development, the
the scale ofthe scale of
of electrolytic
electrolytic
scale electrolytic bath has
has
bath has gradually
bath
gradually
gradually expanded
expanded expanded
from 3 to 10 from 3
kA [33],
from to
3 to 1010 kA
andkA [33],
the[33], and
maximum the maximum
and theelectrolytic
maximumbath electrolytic bath
could reach
electrolytic bath60could reach
kA [34,35].
could 60 kA
So kA
reach 60 far,
[34,35]. So
large-scale far,
rarelarge-scale
earth rare
enterprises earthsuchenterprises
as Ruixin such
Groupas Ruixin
and Group
Qiandong and Qiandong
Group
[34,35]. So far, large-scale rare earth enterprises such as Ruixin Group and Qiandong Group have have Group
already have
used
already
already usedelectrolytic
10 kA-level
used 10 kA-level
10 kA-levelbath
electrolytic bath [36].
[36]. However,
electrolytic bath [36]. However,
because because
of the
However, of the
low level
because of the low
oflow level of
of automation,
automation,
level automation, most
most of themost
rare
of the
earth
of rare earth
the enterprises enterprises are
are still using
rare earth enterprises still
are 6~10 using 6~10 kA
kA electrolytic
still using electrolytic bath [37].
bath [37]. bath [37].
6~10 kA electrolytic
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Metals 2020, 10, x FOR PEER REVIEW 4 of 12

2.2. Metal Thermal Reduction
2.2. Metal Thermal Reduction
Metal thermal reduction refers to the reduction of rare earth compounds into metals at high
Metal thermal
temperatures reduction
by active refers toagents,
metal reducing the reduction of rare
such as Ca, earth
La, and Cecompounds
[38]. Sm, Eu,into
Yb, metals
and Tmathave
high
temperatures
moderate by active
melting point metal reducinghigh
and relatively agents, suchpressure,
vapor as Ca, La,
soand
La Ce [38].
or Ce Sm,relatively
with Eu, Yb, and
lowTm have
vapor
moderate melting point and relatively high vapor pressure, so
pressure are used as reductants, the reduction equation is as follows:La or Ce with relatively low vapor
pressure are used as reductants, the reduction equation is as follows:
+ RE
2La2La 2 O23O=
+ RE 2RE↑ + La22O
3 = 2RE↑ + La O33 (4)
(4)

Y,Y,Gd,
Gd,Tb,
Tb,Dy,
Dy,Ho,
Ho,Er,
Er,Lu
Luare
areprepared
preparedbybycalcium
calciumthermal
thermalreduction,
reduction,the
thereduction
reductionequation
equationisis
asasfollows:
follows:
3Ca + 2ReF3 = 3CaF2 + 2RE (5)
3Ca + 2ReF3 = 3CaF2 + 2RE (5)
Metallic
Metallicimpurities
impuritiessuch
suchasasCa,
Ca,Ni,
Ni,Mo,
Mo,Ti,
Ti,W
Wand
andinterstitial
interstitialimpurities
impuritiesC,C,O,
O,and
andNNmight
mightexist
exist
ininrare earth metals prepared by the above method [39]. The schematic diagram of metal
rare earth metals prepared by the above method [39]. The schematic diagram of metal thermal thermal
reduction
reductionmethod
methodisisshown
shownininFigure
Figure4.4.

Figure4.4.Schematic
Figure Schematicdiagram
diagramofofmetal
metalthermal
thermalreduction.
reduction.

Impuritiesof
Impurities of rare
rare earth metals
metalsarearemainly
mainlyderived
derived from
from rawrawmaterials.
materials. Ni impurity
Ni impurity mainly came
mainly
fromfrom
came the nickel boat.boat.
the nickel Ni concentration
Ni concentration could be reduced
could be reduced fromfrom
0.01% 0.01%to 0.003%
to 0.003% by byreducing
reducing the
temperature of the fluorination process or applying
the temperature of the fluorination process or applying a protective layer ona protective layer on the nickel boat [40].
boat [40].
Impuritiessuch
Impurities such as
as Si, Fe,
Fe, Al,
Al,Mo,
Mo,TiTiwereweremostly
mostly fromfromrarerare
earth oxide
earth and and
oxide reagent materials.
reagent Total
materials.
concentration
Total of impurities
concentration in rare
of impurities earth
in rare metals
earth metalscould be reduced
could be reducedfrom 0.12%
from to less
0.12% than
to less than0.01%
0.01% by
improving the purity of raw materials as well as using analytical reagent
by improving the purity of raw materials as well as using analytical reagent [41]. Oxygen impurity [41]. Oxygen impurity was
mainly
was derived
mainly from
derived fromrawrawmaterials,
materials, reducing
reducingagents,
agents,and andoxidation
oxidationof of rare metals [42,43].
rare earth metals [42,43].
Oxygen concentration
Oxygen concentration could be reduced from 0.1% to less than 0.07% by improving
be reduced from 0.1% to less than 0.07% by improving the purity the purity of raw
ofmaterials [40]. Impurities
raw materials of W and
[40]. Impurities of NbW andwereNb mainly
werefrom mainly metalfrom crucible
metal material. Tungsten
crucible material.
concentration
Tungsten of rare earth
concentration of raremetals
earthcould
metals becould
reduced to less than
be reduced to less0.008%
than by improving
0.008% vacuum
by improving
remelting or vacuum distillation process conditions
vacuum remelting or vacuum distillation process conditions [39]. [39].
UpUptotonow,
now,single
singlefurnace
furnace output
output ofof metal
metal thermal
thermal reduction
reduction hashas gradually
gradually developed
developed fromfrom
100100g
tog 100
to 100 kg [44].
kg [44]. Its advantages
Its advantages are loware investment
low investment and compact
and compact process,process,
but there butare
there
alsoare
somealsoissues
some
issues
such as such
harshasrequirements
harsh requirements on equipment,
on equipment, discontinuous
discontinuous production production
process, process, and generally
and generally higher
higher impurity
impurity concentration
concentration than electrolytic
than electrolytic rare earth rare earth metals.
metals.
InInconclusion,
conclusion,the theresearches
researchesmainly
mainlyfocused
focusedon ontwo
twoaspects:
aspects:purity
purityand andyield.
yield.Purity
Purityisismainly
mainly
concerned with reducing metallic impurities such as Fe, Mg, and Si. The
concerned with reducing metallic impurities such as Fe, Mg, and Si. The concentration of impurities concentration of impurities
canbebe
can reduced
reduced to ato a certain
certain extentextent by adjusting
by adjusting the material
the material and parameters
and technical technical parameters of the
of the equipment.
equipment. However, there are fewer studies on effectively reducing the
However, there are fewer studies on effectively reducing the concentration of interstitial impurities concentration of interstitial
impurities
such as O and such
N, as
andO mechanism
and N, and of mechanism
action remain of action
to beremain
furthertostudied.
be further Yieldstudied. Yield
is mainly is mainly
concerned
concerned
with withconsumption
low energy low energy consumption and high
and high recovery rate.recovery
The gasrate. The gas
tightness tightness ofand
of equipment equipment
automation and
automation degree in preparation process should
degree in preparation process should be more concerned in future. be more concerned in future.
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3.3.Progress
3. Progress in
Progressin Purification
inPurification of
Purificationof Rare
ofRare Earth
RareEarth Metals
EarthMetals
Metals
Whether
Whether molten
Whethermolten salt
moltensalt electrolysis
saltelectrolysis ormetal
electrolysisoror metalthermal
metal thermalreduction,
thermal reduction,
reduction, the
the
the purity
purity
purity ofofof rare
rare
rare earth
earth
earth metals
metals
metals is
isisinin
in a range
aarange of 95.5~99.5%,
rangeofof95.5~99.5%,
95.5~99.5%,which which cannot
whichcannot
cannotmeet meet
meetthe the requirements
therequirements of
requirementsofofhigh high performance
highperformance
performancematerialsmaterials
materials[45].[45].
[45].At At
At present,
present,
present, thethe
the purification
purification
purification methods
methods
methods mainly
mainly
mainly include
include
include vacuum
vacuum
vacuum distillation,
distillation,
distillation, arc melting,
arcmelting,
arc melting, zonezone
zone melting,
melting,
melting, and
and
and solid
solidstate
solid state electromigration
stateelectromigration [46,47].
electromigration[46,47].
[46,47].

3.1. Vacuum
3.1.Vacuum Distillation
VacuumDistillation
Distillation
3.1.
In the process of metal thermal reduction, excessive reducing agent isisusually added to confirm
InInthe
theprocess
processofofmetal
metalthermal
thermalreduction,
reduction,excessive
excessivereducing
reducingagent
agentis usuallyadded
usually addedto toconfirm
confirm
complete reaction.
complete reaction. Therefore,
reaction. Therefore, rare
Therefore, rare earth
rare earth metals
earth metals prepared
metals prepared
prepared by by this
by this method
this method
method havehave high
have high impurity
high impurity
impurity
complete
concentration
concentrationand and should
andshould
shouldbe be purified
bepurified before application.
purifiedbefore
before application. Vacuum
Vacuumdistillation
distillationwas waswidely
widelyused used
concentration application. Vacuum distillation was widely used inin
in industry
industry to remove reductant metals in order to obtain high rare
purity rare earth[48–51].
metals Vacuum
[48–51].
industry totoremove
remove reductant
reductant metals
metals ininorder
order totoobtain
obtain highpurity
high purity earth
rare earth metals
metals [48–51]. Vacuum
Vacuum distillation
distillation meansthatmeans
that that
rare raremetals
earth earth metals are separated
areseparated
separated from impurities
fromimpurities
impurities under under high temperature
hightemperature
temperature and
distillation means rare earth metals are from under high and
and high
highvacuum. vacuum.
vacuum.Figure Figure
Figure55shows 5 shows
showsschematicschematic
schematicdiagram diagram
diagramofofvacuum of vacuum
vacuumdistillation.distillation.
distillation.Vacuum Vacuum
Vacuumdistillation distillation
distillationrequires
requires
high
requires
thatmatrix thatmetal
matrix matrix metalhave
should should have
high high saturated
saturated vapor pressure
vaporpressure
pressure andvapor
vaporand vapor pressure
pressure difference difference
fromthethe
that metal should have high saturated vapor and pressure difference from
from the impurity
impurity element. element.
Figure 6 Figure the
shows 6 shows
vapor the vapor pressures
pressures of rare of rare
earth earth and
elements elements and impurities
impurities at 1600 °C
impurity◦ element. Figure 6 shows the vapor pressures of rare earth elements and impurities at 1600 °C
at 1600
[52]. C [52].
[52].

Figure5.
Figure
Figure 5.5.Schematic
Schematicdiagram
Schematic diagramof
diagram ofvacuum
of vacuumdistillation.
vacuum distillation.
distillation.

6 6 6 6
1010 1010
(a)
(a) (b)(b)
4 4 4 4
1010 1010
2 2 2 2
1010 1010
0 0 0 0
1010 1010
-2 -2 -2 -2
1010 1010
-4 -4 -4 -4
1010 1010
P in Pa

P in Pa
P in Pa

P in Pa

-6 -6
10 -6 -6
10 1010
-8 -8 -8 -8
1010 1010
-10-10 -10-10
1010 1010
-12-12 -12-12
1010 1010
-14-14 -14-14
1010 1010
-16-16 -16-16
1010 1010
-18-18 -18-18
1010 1010
-20-20 -20-20
1010 1010
W W TaTa MoMo TiTi SiSi MnMn NiNi FeFe CrCr AlAl PbPb CaCa MgMg ZnZn ScSc Y Y LaLaCeCePrPrNdNdSmSmEuEuGdGdTbTbDyDyHoHoErErTmTmYbYbLuLu
Impurityelements
Impurity elements Rareearth
Rare earthelements
elements

Figure Vapor
6.6.Vapor pressures of impurities (a) and rare earth elements (b) atat1600
1600 ◦ C.
Figure6.
Figure Vaporpressures
pressuresof
ofimpurities
impurities(a)
(a)and
andrare
rareearth
earthelements
elements(b)
(b)at 1600°C.
°C.

Vacuum
Vacuumdistillation
Vacuum distillation
distillation can
can remove
can remove
remove most metallic
most
most impurities
metallic
metallic and interstitial
impurities
impurities impurities.
andinterstitial
and interstitial In the process
impurities.
impurities. InInthe
the
of distillation,
process of metallic
distillation, impurities
metallic with
impuritieshigh vapor
with pressure
high vapor such as
pressure Ca,
suchMg,as
process of distillation, metallic impurities with high vapor pressure such as Ca, Mg, and Al have and
Ca, Al
Mg,have
and obvious
Al have
removal
obvious effect.
obviousremoval
removalFor example,
effect.
effect. total
Forexample,
For concentration
example, of metallic
totalconcentration
total concentration impurities
ofof in Tb suchinin
metallicimpurities
metallic impurities asTbCa,
Tb Mg,asas
such
such Al, Si,Mg,
Ca,
Ca, Zn,
Mg,
Cr, and
Al,Si,
Al, Mn
Si,Zn, could
Zn,Cr,
Cr,and be
andMn reduced
Mncould from
couldbe 0.065%
bereduced to
reducedfrom less than
from0.065% 0.001%
0.065%totoless [53].
lessthan Metallic
than0.001% impurities
0.001%[53].
[53].Metallicsuch as Ta,
Metallicimpurities W,
impurities
Mo, Nb, and
suchasasTa,
such Ta,W, Ti
W,Mo,and
Mo,Nb,interstitial
Nb,and impurities
andTiTiand such
andinterstitial as C,
interstitialimpuritiesO, and
impuritiessuch N that
suchasasC,C,O,exist
O,and in the
andNNthat form
thatexist of compounds
existininthe
theform
formofof
remained at the
compoundsremained
compounds bottom
remainedatattheof tungsten
thebottom crucible
bottomofoftungsten [54–56].
tungstencrucible This was
crucible[54–56]. mainly
[54–56].This
Thiswas because
wasmainly the
mainlybecausevapor
becausethe pressure
thevapor
vapor
pressureofofthe
pressure theimpurities
impuritiesisismuch
muchlower
lowerthan
thanthat
thatofofthe
therare
rareearth
earthmetals.
metals.W
Wconcentration
concentrationofofGd
Gd
could be reduced from 0.018% to 0.005% after vacuum distillation [57]. Interstitial
could be reduced from 0.018% to 0.005% after vacuum distillation [57]. Interstitial impurity impurity
Metals 2020, 10, 1376 6 of 13

Metals 2020, 10, x FOR PEER REVIEW 6 of 12

of the impurities is much lower than that of the rare earth metals. W concentration of Gd could be
concentration
reduced from of Sm was
0.018% reduced
to 0.005% to 0.0045%,
after vacuum and that of [57].
distillation Yb reduced to 0.0051%
Interstitial impurity[58]. The removal
concentration of
effect
Sm wasof metallic
reducedimpurities
to 0.0045%, with andsmall
that vapor pressureto
of Yb reduced difference
0.0051% from[58]. matrix metal was
The removal not
effect ofobvious,
metallic
such as Fe and
impurities withCu.
small vapor pressure difference from matrix metal was not obvious, such as Fe and Cu.
Vacuum
Vacuum distillation
distillationhashasthe theadvantages
advantages of of
relatively high
relatively production
high productionefficiency and and
efficiency yield,yield,
but
impurities segregation
but impurities is prevalent
segregation is prevalent in prepared
in preparedrare earth
rare earthmetals
metals[59].
[59].Rare
Rareearth
earthmetal
metalpurification
purification
by vacuum distillation
by vacuum distillationisisstill
stillinin
thethe stage
stage of small
of small batchbatch
trial trial production,
production, and
and the the single
single furnacefurnace
output
output is only 1~5
is only 1~5 kg [60]. kg [60].

3.2. Arc
3.2. Arc Melting
Melting
Arc melting technology
Arc technology is is aa common
commonmethodmethodtotopurify
purifymetals
metalsandandalloys.
alloys.ItItuses
uses electric energy
electric energy to
generate
to generate electric arcarc
electric between
between electrode
electrodeandandmolten material
molten to melt
material the metal.
to melt Metallic
the metal. impurities
Metallic with
impurities
high high
with saturated vaporvapor
saturated pressure and interstitial
pressure impurities
and interstitial can becan
impurities effectively removed
be effectively by using
removed byplasma
using
arc as heat
plasma source
arc as heat to melt to
source metal
meltmaterials. At present,
metal materials. the working
At present, gas used
the working gasinused
this method is mainly
in this method is
Ar, H2 , Ar,
mainly N2 , H
He 2, and the and
N2, He mixture of aboveofgases.
the mixture aboveIngases.
recentInyears, researchers
recent have found
years, researchers havethat usingthat
found the
mixture
using theof Ar andofHAr
mixture 2 as theHworking
and gas could
2 as the working gassignificantly improve
could significantly the purification
improve effect of
the purification rare
effect
earth
of raremetals. This melting
earth metals. method
This melting is called
method hydrogen
is called plasma
hydrogen arc melting.
plasma In theIn
arc melting. present work,work,
the present it can
itbecan
proved that when
be proved the temperature
that when the temperaturereachesreaches
5000 K,5000
the dissociation of H2 isofup
K, the dissociation Hto2 isabove
up to 95%
above[61,62].
95%
The activated hydrogen atoms could combine with oxygen and nitrogen.
[61,62]. The activated hydrogen atoms could combine with oxygen and nitrogen. The reactions that The reactions that occur in
this system
occur in thisare as follows:
system are as follows:
H2 = H + H (6)
H2 = H + H (6)
O (in metal) + 2H = H2 O (7)
O (in metal) + 2H = H2O (7)
N (in metal) + 3H = NH3 (8)
N (in metal) + 3H = NH3 (8)
This method
This method has has been
been successfully
successfully applied
applied to to the
thepurification
purification of
of rare
rare earth
earthmetals
metalssuch suchasasLa,
La,Ce,
Ce,
Tb, and
Tb, and GdGd [63,64].
[63,64]. Figure
Figure 77 is
is the
the schematic
schematic diagram
diagram of of hydrogen
hydrogen plasma
plasma arcarc melting.
melting.

Figure
Figure 7.
7. Schematic
Schematicdiagram
diagramof
ofhydrogen
hydrogen plasma
plasma arc
arc melting.
melting.

Metallic impuritieswith
Metallic impurities withhigh
high saturated
saturated vapor
vapor pressure
pressure such assuch
Ca, as
Mg,Ca,andMg, and Al
Al could could be
be effectively
effectively
removed byremoved by arc
arc melting. Formelting.
example,For example,
total total concentration
concentration of metallic
of metallic impurities of Tbimpurities
decreasedoffrom
Tb
decreased from 0.438%
0.438% to 0.0580% after arctomelting
0.0580% after
[63]. arc melting
Hydrogen plasma[63]. Hydrogen
has high chemical plasma has Ithigh
reactivity. chemical
can react with
reactivity. It can
carbon, oxygen, react with
nitrogen, carbon,
and other oxygen,
impurities nitrogen,
to form gaseousandcompounds,
other impurities to formimpurities
thus promoting gaseous
compounds,
clearance [65].thus
Whenpromoting
Tb and LaNiimpurities clearance
5 alloy were melted [65]. When Tbplasma,
in hydrogen and LaNi 5 alloy
carbon were melted
concentration in
of Tb
hydrogen
decreased plasma,
from 0.03% carbon concentration
to 0.0017% [63], andofcarbon
Tb decreased fromof0.03%
concentration LaNi5toalloy
0.0017% [63], from
decreased and carbon
0.018%
concentration
to 0.0014% [64]. of The
LaNiconcentration
5 alloy decreasedof Ofrom
and N 0.018%
of Tb to 0.0014% from
decreased [64].The
0.05%concentration of O and N of
to 0.0015% [66].
Tb decreased
Hydrogen from 0.05%
plasma arctomelting
0.0015%[66].
have a good removal effect on metallic impurities and interstitial
Hydrogen
impurities. Theplasma
removalarc degree
meltingofhave a good removal
interstitial impuritieseffect on metallicbetter
is obviously impurities and interstitial
than other methods.
impurities. The removal
However, because of high degree of interstitial
temperature and high impurities is obviously
vacuum required better than
by the process, otherplasma
hydrogen methods.arc
However, because of high temperature and high vacuum required by the process, hydrogen plasma
arc melting technology for rare earth metals is still in the laboratory research stage, and its single
furnace output is only 10~200 g [67,68].
Metals 2020, 10, 1376 7 of 13

melting technology for rare earth metals is still in the laboratory research stage, and its single furnace
output is only 10~200 g [67,68].
Metals 2020, 10, x FOR PEER REVIEW 7 of 12
3.3. Zone Melting
3.3. Zone
ZoneMelting
melting is a process of redistributing impurities by making use of their different solubility in
solid and liquid phases. In this operation, the researchers slowly melt the metal bar by moving the
Zone melting is a process of redistributing impurities by making use of their different solubility
induction coil from one end of the metal bar to the other. This process allows multiple directional
in solid and liquid phases. In this operation, the researchers slowly melt the metal bar by moving the
movements to accumulate impurities at both ends of the metal bar. Equilibrium distribution coefficient
induction coil from one end of the metal bar to the other. This process allows multiple directional
refers to the ratio of solute concentration in the solid and liquid phases when the solid and liquid
movements to accumulate impurities at both ends of the metal bar. Equilibrium distribution
systems reach equilibrium [69], and defined as:
coefficient refers to the ratio of solute concentration in the solid and liquid phases when the solid and
liquid systems reach equilibrium [69], and defined as:
K = CS /CL (9)
K = CS/CL (9)
where CS and CL are denoted as impurity concentration in solid phase and impurity concentration
where CS and CL are denoted as impurity concentration in solid phase and impurity concentration in
in the liquid phase respectively. Impurities whose K < 1 move toward the end of the metal bar,
the liquid phase respectively. Impurities whose K < 1 move toward the end of the metal bar, and
and impurities whose K > 1 move toward the beginning end of the metal bar. Figure 8 is the schematic
impurities whose K > 1 move toward the beginning end of the metal bar. Figure 8 is the schematic
diagram of plasma arc zone melting.
diagram of plasma arc zone melting.

Figure 8. Schematic
Figure 8. Schematic diagram
diagram of
of plasma
plasma arc
arc zone
zone melting.
melting.

meltinghas
Zone melting hasbeen
beenwidely
widely used
used to to purify
purify semiconductor
semiconductor materials
materials suchsuch
as Si,asSb,Si,Te,Sb,
andTe,metal
and
metal materials
materials such as suchZnasand
Zn Cuand[70].
Cu [70]. Researchers
Researchers have have applied
applied zonemelting
zone meltingtotopurify
purify rare rare earth
metals, and the results showed showed thatthat there
there were obvious
obvious segregation
segregation in in the
the rare
rare earth
earth metals
metals [71].
[71].
Metallic impurities
impurities withwith high
highsaturated
saturatedvaporvaporpressure
pressuresuch suchasasCa,
Ca,Mg,
Mg,Zn,Zn, MnMn could
could bebe reduced
reduced to
lessless
to than 0.0001%.
than Fe, Cu,
0.0001%. Fe,Al,
Cu,Si Al,
couldSi be enriched
could at the end
be enriched at as
thethe
endmelted
as thezone moves
melted [72].moves
zone Interstitial
[72].
impurities impurities
Interstitial such as O and suchN aswere
O and enriched
N were at the beginning
enriched [73]. Impurities
at the beginning such as Csuch
[73]. Impurities andas S showed
C and S
differentdifferent
showed migration patternspatterns
migration in different rare earth
in different raremetals. After zone
earth metals. Aftermelting, impurities
zone melting, impuritiessuch such
as C
and S of La were enriched at the beginning, while C and S of Ce were enriched
as C and S of La were enriched at the beginning, while C and S of Ce were enriched at the end [73]. at the end [73].
meltinghad
Zone melting had obvious
obvious migration
migration effecteffect
on some on metallic
some metallic
impuritiesimpurities and impurities.
and interstitial interstitial
impurities.different
However, However, different
migration migration
rules rules usually
of impurities of impurities usually
appeared appeared
in different rareinearth
different
metals, rare
andearth
the
metals, and the purification mechanism needs to be further studied. The principle
purification mechanism needs to be further studied. The principle of zone melting is the redistribution of zone melting is
theimpurities
of redistribution of impurities
rather than actual rather
removalthan of
actual removal In
impurities. of impurities. In order
order to achieve to achieve
excellent excellent
purification
purification
effect, nearlyeffect, nearly
20 times 20 timesmelting
of repeated of repeated melting
of rare earth of rare earth
metals metals are
are needed. needed.the
Moreover, Moreover,
purification the
purification
efficiency efficiency
of zone meltingof zone
is low,melting
and theissingle
low, and the single
furnace outputfurnace output
of rare earth of rare
metals earthabout
is only metals30 is
g.
only aboutzone
Therefore, 30 g. melting
Therefore, zoneused
is only melting is only
as the final used
method as the final method
to purify to purify
small batches smallpurity
of high batches of
rare
high purity
earth metalsrare earth metals [73,74].
[73,74].

3.4. Solid State Electromigration

Solid state electromigration means that under high vacuum conditions, the metal bar is placed
between two electrodes and applied with direct current for aa longlong time.
time. The joule heat make the
temperature of the test bar reach 0.8~0.9 times of the metal melting point and keep the test bar from
melting. Under the action of direct current, atoms are not neutral. In general, one atom can acquire
more or less positive charge than the other, resulting in different ionization behaviors. Moreover,
atoms can be affected by electrostatic force, electron collision friction and cavity friction [75], and
defined as:
FS = eEZ0 (10)
Metals 2020, 10, 1376 8 of 13

melting. Under the action of direct current, atoms are not neutral. In general, one atom can acquire more
or less positive charge than the other, resulting in different ionization behaviors. Moreover, atoms can
be affected by electrostatic force, electron collision friction and cavity friction [75], and defined as:

Metals 2020, 10, x FOR PEER REVIEW FS = eEZ0 8(10)

of 12

Fe F=e −eEn
= -eEne leeleσσee (11)
(11)
FhF=h =eEnh lhhlσ
eEn hσ
hh (12)
(12)
F = FS + Fe + Fh = eEZ0 − eEne le σe + eEnh lh σh = eEZ* (13)
F = FS + Fe + Fh = eEZ0 − eEneleσe + eEnhlhσh = eEZ* (13)
where e is elementary charge in units of C; E is electric field intensity in units of V·m−1−1; Z0 0is the ion
where e is elementary charge in units of C; E is electric field intensity in units of V·m ; Z is the ion
valence; n is unit volume electron; l is the electron mean free path; σ is the electron scattering cross
valence; n is unit volume electron; l is the electron mean free path; σ is the electron scattering cross
section; Z* is effective valence.
section; Z* is effective valence.
Atoms with more positive charge migrate to the cathode extreme, and atoms with more negative
Atoms with more positive charge migrate to the cathode extreme, and atoms with more negative
charge migrate to the anode extreme. In the purification process, the migration rate of impurity atoms is
charge migrate to the anode extreme. In the purification process, the migration rate of impurity atoms
higher than that of matrix atoms, so the impurities can be redistributed in matrix metal. Metals exhibit
is higher than that of matrix atoms, so the impurities can be redistributed in matrix metal. Metals
different crystal structures at different temperatures. Interstitial impurities show different migration
exhibit different crystal structures at different temperatures. Interstitial impurities show different
patterns in different crystal structures. For example, when Pr is in double hexagonal closest packed
migration patterns in different crystal structures. For example, when Pr is in double hexagonal closest
structure (named as DHCP), H, N, and O atoms can enter the intercellular space except C. However,
packed structure (named as DHCP), H, N, and O atoms can enter the intercellular space except C.
when Pr is transformed into BCC structure, all atoms cannot enter the intercellular space except H [76].
However, when Pr is transformed into BCC structure, all atoms cannot enter the intercellular space
Therefore, researchers attempt to remove interstitial impurities by solid state electromigration at crystal
except H [76]. Therefore, researchers attempt to remove interstitial impurities by solid state
temperature with a high migration rate of interstitial impurities [77,78]. Figure 9 is the schematic
electromigration at crystal temperature with a high migration rate of interstitial impurities [77,78].
diagram of rare earth prepared by solid state electromigration.
Figure 9 is the schematic diagram of rare earth prepared by solid state electromigration.

Figure9.9.Schematic
Figure Schematicdiagram
diagramofofsolid
solidstate
stateelectromigration.
electromigration.

Forexample,
For example, after
after 216 h216 h ofvacuum
of high high andvacuum and high temperature
high temperature electromigration,electromigration,
the concentration the
ofconcentration
impurities suchof impurities
as Al and such Si of as
Pr Al and Si from
decreased of Pr 0.04%
decreased from and
to 0.02%, 0.04% to concentration
total 0.02%, and total of
concentration of Fe and Ni decreased from 0.05% to 0.002% [79]. The concentration
Fe and Ni decreased from 0.05% to 0.002% [79]. The concentration of interstitial impurities was of interstitial
impurities
reduced fromwas reduced
0.0239% from 0.0239%
to 0.0049%, to 0.0049%,
among which among
the oxygen which thewas
concentration oxygen
reducedconcentration was
to 0.0022% [80].
reduced to 0.0022% [80]. Solid state electromigration had significant removal effect
Solid state electromigration had significant removal effect on most metallic impurities and interstitial on most metallic
impurities[81],
impurities andbut
interstitial
not obvious impurities
removal [81], butonnot
effect obvious
carbon and removal
nitrogen effect on carbon
impurities [82,83].and nitrogen
Solid state
impurities [82,83].
electromigration wasSolid state electromigration
essentially was essentially
a process of impurities a processand
redistribution, of impurities redistribution,
it did not really remove
and it did not
impurities, really
which willremove
seriously impurities,
affect thewhich will seriously
subsequent affect
use of rare themetals.
earth subsequentSinceuse
theofsolid
rare state
earth
metals. Since the
electromigration solid required
process state electromigration processand
high vacuum degree required
energyhigh vacuum of
consumption degree and energy
equipment. It is
consumption of equipment. It is difficult to achieve large-scale industrial production, so this method
is mainly used as the final purification method to produce small amount of ultra-high purity metals
[84].
From the above, it is not possible to remove all impurities of rare earth metals simultaneously
by any of the above methods. Therefore, after comprehensive consideration of the impurity types,
purity requirements and removal effect of impurities, it should be considered that several purification
Metals 2020, 10, 1376 9 of 13

difficult to achieve large-scale industrial production, so this method is mainly used as the final
purification method to produce small amount of ultra-high purity metals [84].
From the above, it is not possible to remove all impurities of rare earth metals simultaneously
by any of the above methods. Therefore, after comprehensive consideration of the impurity types,
purity requirements and removal effect of impurities, it should be considered that several purification
methods should be combined to remove the impurities. For example, vacuum distillation combined
with arc melting can improve the density and purity of rare earth metals. Ultralow oxygen concentration
of rare earth metals can be prepared by the combination of arc melting and solid state electromigration.

4. Summary and Prospect

In the past 60 years of development, remarkable achievements have been achieved in scientific
research and industrial application of rare earth elements, forming a relatively well-developed rare
earth industrial system. But at the same time, it should also be noted that there are issues in many
areas that need to be solved.

(1) Molten salt electrolysis and metal thermal reduction possess high efficiency and yield, but low
purity of rare earth metals and high energy consumption are generally non-negligible.
(2) The preparation process of rare earth metals is mainly a manual operation with low automation
degree and severe environmental pollution issue.
(3) Deep purification ability of rare earth metals is insufficient, and the industrialization is limited to
the use of vacuum distillation, which is difficult to meet the needs of high technology development.

Consequently, expensive price of high-purity rare earth metals appeared and limit their application.
Therefore, the following directions are the focus of our attention in future:

(1) The impurity concentration of rare earth metal should be further reduced so as to provide high
purity starting material for the purification process.
(2) A combination of various purification methods should be chosen to remove the impurities for
considering the kinds and uses of rare earth metals.
(3) Purification methods suitable for mass production such as vacuum levitation melting and electron
beam melting should be developed and researched.

Author Contributions: Conceptualization, H.L. and Y.L.; methodology, H.L. and Y.L.; software, H.L.; validation,
H.Y.; formal analysis, H.L.; investigation, H.L.; resources, D.L.; data curation, H.Y.; writing—original
draft preparation, H.L.; writing—review and editing, H.Y.; visualization, Y.Z.; supervision, Y.L. and D.L.;
project administration, Y.Z.; funding acquisition, Y.L. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was supported by Strategic Priority Research Program of the Chinese Academy of Sciences
funded by Chinese Academy of Sciences (ACS) (XDC04010200). This work was also supported by Inner Mongolia
Science and Technology Major Project funded by Inner Mongolia Science and Technology Department (2017B001).
Conflicts of Interest: The authors declare no conflict of interest.

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